2-amino-5-nitro-1, 3, 4-thiadiazole azo dyes



United States Patent Z-AMINO-S-"NITRO-1,3,4-THIADIAZOLE AZO DYES Edmund B. Towne and Joseph-B. Dickey, Kingsport,

Tenn., assignors to Eastman "Kodak Company, Rochester, N. Y acorpora'tiou of New Jersey' No Drawing. Application August 27, 1952, Serial No. 306,712 6-Claims. (Cl. 260-158) This invention relates to.Z-amino S-nitro-l,3,4-thiadiazole, the process for its preparation and to azo and sulfathiadiazole compounds prepared therefrom.

2-amino-5-nitro-l,3,4-thiadiazole, as fully shown hereinafter, is a valuable intermediate for the preparation of azo dye compounds useful for coloring various textile materials, especially cellulose acetate textile materials. Z-amino-S-nitro-1,3,4-thiadiazole also possesses interesting possibilities in the pharmaceuticalfield"because sulfathiadiazole compounds "having the general formula:

II wherein "Q represents a nine group or an amino group are readily prepared therefrom. 2-amino-5-nitro-1,3,-4- "thiadiazolelikewis-e may 'havedirect utility as a medicinal whereinR representsanalkylgroup havingl-to '4, inclu- .sive,.=carbon atoms, .a vhydroxyalkyl group having 2 to 4, inclusive, .carbon atoms, an alkoxyalkyl group having 3 to 4, inclusive, carbon atoms, a fl-cyanoethyl group, a --CH2CH2COOCH3. group,.a CH2CH2COOC2H5 group, a 2,2-difluroethy1 group, a'2,'2-"difiuoro-n-propyl group, a 13,,3-difluoropropyl group, a 3,3:dilluoro-n-butyl group,

group, R1 represents a hydroxyalkyl group having 2104, inclusive, carbon atoms or an :acetoxyethyl group, X

',.represents :a hydrogen atom, a methoxy group :or an ethoxygroup and Y represents a hydrogensatom, a :methyl ,group, .a brominebatom, a chlorine .atom, a methoxy -zgr0up, an .cthoxy group, an :acetylamino group, a propionylamino grouprorabutyrylaminogroup. 1

The azo compounds .of our -.invention are useful to coloring textile materials made of or containing a cellu- Ilose carboxylic acid "esterhaVin'g'Z to 4 carbon atoms in the acid groups'thereof. They are especially of use .for

- the coloration of cellulose acetate textile materials.

'When applied to the aforesaid textilematerials,;they give orangedo-red dyeings which for the'most part have good fastn'ess to both light and gas. The azo compounds .of our inventionalso color wool, silk, nylon, polyethylene nerephthalate and modified po'lyacrylonitrile textile materials similar shades.

By cellulose alkyL'carboxylic acid esters having two to .tour .carbon atoms in the acid groups thereof, .we mean A further object .is to prepare.

stirring. Following this,

Patented Apr. 30, 1957 'ice to include, for example, tb'Oih hydrolyzed and unhydrolyzed cellulose acetate, cellulosev propionate, cellulose butyrate, cellulose.acetate-propionate and cellulose ace- I tate-butyrate.

The azo compounds .of our invention are prepared by diazotizing 2-amino-5-nitro-1,3,4-thiadiazole and coupling the diazonium compound obtained with a compound having the formula:

EXAMPLE 1 Preparation of Z-amino-S-nitro-J,3,4-thiadiaz0le 10 grams of 2-amino-l,3,4-thiadiazole were dissolved in 50 cc. of fuming nitric-acid at room temperature. The reaction mixture resulting was then heated to 40 C. and maintained at this temperature for l to 2 hours, while the reaction mixture was drowned on ice and filtered. 2-amino-5-nitro- 1,3,4- thiadiazole was collected on the filter as a bright yellow crystalline product and was washed with water until neutral and then dried. The dried product weighed 8.5 grams and had amelting point of 173 C. Upon crystallization from ethyl alcohol, the Z-amino-S nitro-LSA- thiadiazole reaction product had a melting point of 178* C.

Z-amino-l,3,4 thiadiazole is a known compound.

compound having a melting point of 191 C.

"rise to 65 C. 'The resulting solution was then cooled 60 to 5 and 20' cc. of .a mixture consisting of 3 cc. of 'propionic acid and 17 cc. ofaceticacid Were addeddropwise, with stirring, while allowing the temperature to rise to 15 C. and maintaining it at this temperature during the remainder of the addition.

.B. .Diazotization The nitrosyl sulfiurioacid' mixture prepared. as. described above was cooled to 0 -C.-.-5 C. and then 2 grams of Z-amino-S-nitro-1,3,4-thiadiazole were addedportionwise, while stirring, after which '20 cc. of a propionic-acetic acid mixture prepared as described above :were added awhile ikeeping the-temperature of the-reaction mixture {at -.-0- :C.-"5 C; The reaction mixture thus obtainedwas on the filter. washed well with water and dried. 0.7 gram of the dye thenstirred at C.- C. for 2 hours and excess sodium nitrite present was destroyed by adding 0.5 gram of urea. A clear diazonium solution was obtained.

C. Coupling above were added, with stirring, at 0 C.5 C. to a solution of 0.84 gram of N-ethyl-N13 -dihydroxypropylm-toluidine in cc. of a 1:6 mixture of propionic-acetic acid (i. e. 1 part by volume of propionic acid to 6 parts by volume of acetic acid) cooled in an ice bath. After a short time, the reaction mixture was made neutral to Congo paper by adding sodium acetate portionwise and the coupling reaction was allowed to proceed for 20-30 minutes, after which the reaction mixture was poured into ice water. After stirring a short time, the reaction mixture was filtered to recover the dye compound formed The dye compound thus obtained was compound having the formula:

was obtained. This compound has excellent afiinity for cellulose acetate textile materials and colors them bright salmon pink shades having excellent fastness to light and gas. The light fastness of the dyeings obtained with this compound on nylon textile materials is likewise exceptionally good.

EXAMPLE 3 have excellent fastness to light and gas was obtained.

The compound of this example gives dyeings on nylon textile materials which have remarkable fastness to light.

EXAMPLE 4 10 cc. of the 2-amino-5-nitro-1,3,4-thiadiazole .dia-

zonium solution prepared as described in Example 2 were coupled with a solution of 0.86 gram of N,N-di-fl-hydroxyethyl-m-chloroaniline. Coupling and recovery of the dye compound formed were carried out in accordance EXAMPLES 10 cc. of a Z-amino-S-nitro-1,3,4-thiadiazole diazonium solution prepared as described in Example 2 were coupled with a solution of 0.88 gram of N-ethyl-N-pacetoxyethyl-m-toluidine. Coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 2. A

good yield of a compound which colors cellulose acetate and nylon textile materials pinkish-orange shades having excellent fastness to light and gas was obtained.

EXAMPLE 6 10 cc. of a 2-amino-5-nitro-1,3,4-thiadiaxole diazonium solution prepared as described in Example 2 were coupled with a solution of 0.86 gram of N-[i-hydroxyethyl-N2,2 difluoroethyl-m-toluidine in 10cc; of a 1:6

mixture of propionic-acetic acid. Coupling and recovery of the dye compound formed were carried out in accordance with the procedure described in Example 2. The dye compound obtained colors cellulose acetae and nylon textile materials orange shades having excellent fastness to light and gas.

EXAMPLE 7 10 cc. of a 2-amino-5-nitro-1,3,4-thiadiazole diazonium solution prepared as described in Example 2 were coupled with a solution of 0.88 gram of N-ethyl-N- CHzCHzCOOCI-Ia-m-tOluidiue in 10 cc. of a 1:6 mixture of propionic-acetic acid. Coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 2. The dye compound obtained colors cellulose acetate and nylon textile materials bright orange-pink shades having excellent fastness to light and gas.

EXAMPLE 8 10 cc. of a 2-amino5-nitro-l,3,4-thiadiazole diazonium solution prepared as described in Example 2 were coupled with a solution of 0.99 gram of N-fi-hydroxyethyl-N-3,3,3-trifluoropropyl-m-toluidine in 10 cc. of a 1:6 mixture of propionic-acetic acid. Coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 2. The dye compound obtained colors cellulose acetate and nylon textile materials bright orange shades having excellent fastness to light and gas.

EXAMPLE 9 10 cc. of a Z-am-ino-S-nitro-1,3,4'thiadiazole diazonium solution prepared as described in Example 2 were coupled with a solution of 0.89 gram of N-ethyl-N-p- V methyl-my-dihydroxypropyl-m-toluidine in 10 cc. of a.

1:6 mixture of propionic-acetic acid. Coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 2. The dye compound obtained colors cellulose acetate textile materials pinkish-orange shades.

EXAMPLE 10 with a solution of 0.90 gram of N,N-di-p-hydroxyethyl- Z-methoxy-S-chloroaniline in 10 cc. of a 1:6 mixture of propionic-acetic acid. Coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 2. The dye compound obtained colors cellulose acetate textile materials pinkish-red shades.

EXAMPLE 11 10 cc. of a Z-amino-S-nitro-l,3,4-thiadiazole diazonium solution prepared as described in Example 2 were coupled with a solution of 0.96 gram of N-fl,y-dihydroxypropyl- N-p-methoxyethyl-m-toluidine in 10 cc. of a 1:6 mixture of propionic-acetic acid. Coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 2. The dye compound obtained colors cellulose acetate textile materials pinkish-orange shades.

EXAMPLE 12 10 cc. of a Z-amino-S-nitro-1,3,4-thiadiazole diazonium solution prepared as described in Example 2 were coupled with a solution of 0.92 gram of N-2,2-difiuoro-n-propyl- N-B-hydroxypropylaniline in 10 cc. of a 1:6 mixture of propionic-acetic acid. Coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 2. The dye compound obtained colors cellulose acetate textile materials pinkish-orange shades.

EXAMPLE 13 10 cc. of a 2-amino-5-nitro1,3,4-thiadiazole diazonium areas e1 solution prepared as described in Example 2'were coupled 'witlita solution of0.94'gram= of Nn-propyl-N -methoxy- B-hydroxypropyl metoluidinein 10 cc. of a- 1.:6-- mixture of propionic-acetic acid. Couplingand recovery of the dye compoundformed were carried out 'in accordance with the general procedure describedinExample 2.. The dye compound obtained colors cellulose acetate textile materials pinkish-orange shades.

EXAMPLE 14 10 cc. of a 2-arnino-5rnit'ro-1,3,4-thiadiazole diazonium solution preparedas' described in Example 2 werecoupled with a solution of 0.88 gram of N-B,' -dihydroxypropyl- 7-methyltetrahydroquinoline in 10. cc. of a 1:6. mixture of propionic-acetic acid. Coupling and recovery of the dye compound formed were carried out in accordance with the general procedure described in Example 2. The dye compound; obtained has. the formula:

C|1H2CHE0HOH2OH N -H3 CH2 No2o CN=N I it 0 Ha It colors cellulose acetate textile materials red shades.

EXAMPLE l6 cc. of. a Z-amino-S-nitro-lfi.4-thiadiazolediazonium solution prepared as described in Example 2 were coupled with a solution of 0.90 gram of N-Qy-dihydroxypropyl- 7-methylbenz0morpholine in 10 cc. of a 1:6 mixture of propionic-acetic acid. Coupling and recovery of the dye compound. formed were carried' out in accordance with the general procedure described in Example 2. The dye compound obtained has the formula:

It colors cellulose acetate textile materials red shades.

EXAMPLE 17 8.0 grams (0.026 mole) of 2-sulfanilamido-5-nitro- 1,3,4-thiadiazole were added gradually to a stirred suspension of 25 grams of iron powder in 80 cc. of 95% ethanol containing 1 cc. of 1:1 hydrochloric acid. After addition was complete, stirring and refluxing was continued for six hours. The reaction mixture was neutralized with dilute sodium hydroxide, filtered hot, and diluted with five volumes of water. The crude product that crystallized out (4.5 grams) was purified from aqueous ethyl alcohol under a nitrogen atmosphere yielding white crystals of 2-sulfanilamido-5-amino-1,3,4-thiadiazole.

EXAMPLE 18 7.7 grams (0.05 mole) of 2-amino-5-nitro-1,3,4-thiadiazole were dissolved in 20 cc. of pyridine and 12.7 grams of acetyl-sulfanilyl chloride were added slowly, with stirring, at such a rate that the temperature did not exceed 50 C. The reaction mixture was then heated on a steam bath for 1 hour. To this was added a solution and the heati'ngzwastcontinuedi for: as short time;

of 1.2 grams: (.0:05m'ole)% of. NaQH. in 1'55 cc. of. water Drowning' the: solution in water; filtering-1 and drying; yielded 12.3 grams ofi crude yellow crystals of; Z N-acetyhsulfanilarni-do -S-nitrw1,3,4-thiadiazole;

R'efluxing product (0.1035 mole): witlr 315 gramsio'f 'Na'OH in 40 cc. .oflwater; dilutingandineutralizingzyielded 8.0 gran-Isv of yellow; crystalline 2-sul fanilamido=5-nitro- 1',3,4-th'iadiazole' which may be crystallized from acetic The compounds tabulated. hereinafter further illustrate thecompounds of. our invention. These; compounds: are prepared; by dia'zotizin'g 2aamino=5-nitr0+l,3,4 thiadiazole and coupling the diazoniumi compound obtained with: the coupling? components: named hereinafter. The color given istliat whicha thewompoundscol'or cellulose acetate textile materials. The diazotizationgcoupling andsmecovery operations are carried out in accordance: with: the

" procedure described herei'nbefore..

Coupling Component Color 1 N,N; dihydroxyethylm acetylarnino pinkish aniline. orange: 2 N,N d1.- fl.--hydrox-yei;hyl- 2-methoxy- 5 red.

acetyl'aminoanilin'e'.

N,N di fl hydroxyethyl 2 methoxy 5 Do.

methylanilme. N,Nfi di I? hydroxyethyl 2,5 dimethoxypinkish-red.

an me. N,N di-- 18 hydroxyethy-lf- 2,51- dieth'oxy-- Do. N i n1 n1 1 N s m 1 k me oxye y me ew in ishdihydroxy-propyl-m-toluldine. y p orange. N ethoxyethyl N fl hydroxyethyl- Do.

. an 9.. 8 N'- CEzGHaGOOCH': N fl,"y'- dihydroxy' orange-pink.

propyl-n -tolul'dlnea 9. NtdmydroX pIopyL- N fi ecetoxypinkish ethylamlln'e: orange, 10-...-." N Q: hydroxyethyl N 6- hydroxybntylt Do.

aniline. N- B'- hydroxyethyP- N B;'y'- dlnydro'xy: Do.

propyl-m-toluidine. N n--- propyl- N fl hydroayethyl-- m Do. toluidine. 4 13-; c. N n=- propyl- N 6w, -dihydroxypropyl- Do:

m-toluidlne. 14'. N- n*- propyl N 8'- methyl {3, dihy- Do.

droxypropyl=m-toluidine: 15 N 13, dlhydroxypropyl N 3,3- dlfluoro- Do.

n-butyl-m-toluidine: 16; N B hydroxyethyl N 2;2;2 trifiuorororange.

ethylaniltne. I p 17. N B hydroxyethyl N 2,2 difluoro n D02 propylamline. 18;. N fl hydroxyethyl N 3,3 difluoropinkishpropyl-m-toluidine; orange: 19;. a N B- hydroxyethyl N 2,2 difluoro-n orange;

propylaniline. 20 N B hydroxyethyl N 3,3 difluoro n pinkishbutylaniline. orange. 21 N g hydroxyethyl N fl cyanoethylorange.

e. 22 N 3151 butyl N 5, dihydroxypropyl- Do.

an e. 23 N B hydroxypropyl- N B- hydroxyethyl- Do.

aniline. 24 N-methy1-N-n-propylanillne Do. N CHgCHzCOOOzHn N B hydroxy- Do.

ethylaniline. N,N-di-fl-hydroxypropylanlllne Do. N,N dl fl hydroxyethyl m bromo- Do.

aniline. N,N di Q hydroxyethyl m n proplopinkishnylamlnoaniline. orange. N,N di fi hydroxyethyl m n butyryl- Do.

aminoaniline. N 5, dihydroxypropyl 2,7 dlmethylred.

tetrahydroquinoline. N B hydroxyethyl 2 methyltetrahydro- Do.

quinoline. N 18, dihydroxypropyl 2,5 dlmethyl- Do.

benzomorpholine. N 5, dihydroxypropyl 2,7 dimethyl- Do.

benzomorpholine. N methyl N 5, dlhydroxypropyl m orange.

toluidine. N,N-di-flllydroxypropyl-m-toluldlne pinkishorange N,N-di- -hydroxypropyl-m-toluidlne. Do. N n propyl N 'y methoxy-B'hydroxy- Do.

m-tolu' in N,N-dimethyl-m-tolui N-ethyl-N-flhydroxyethylaniline Do.

N,N di B hydroxypropyl 2 methoxy red.

5-methylaniline. 42 N,N di fl hydroxyethyl 2 ethoxy 5 Do.

chloroanillne.

The azo dye compounds of our invention can be applied to the textile materials named hereinbefore in the form of an aqueous dispersion and are ordinarily so applied. To illustrate, the dye compound is finely ground with a dispersing agent such as sodium lignum sulfonate, Turkey red oil, soap, or an oleyl glyceryl sulfate and the resulting mixture is dispersed in water. The dye bath thus prepared is heated to a temperature approximating 45 C.-55 C. and the textile material to be dyed is immersed in the dyebath, following which the temperature is gradually raised to 80 C.90 C. and maintained at this temperature until dyeing is complete, usually onehalf to two hours. From time to time throughout the dyeing operation, the material is worked to promote even dyeing. Upon completion of the dyeing operation, the textile material is removed from the dyebath, washed with an aqueous soap solution, rinsed well with water and dried.

Widely varying amounts of dye can be used in the dyeing operation. The amount of dye used can be, for example, /3 to 3% (by weight) of that of the textile material although lesser or greater amounts of dye can be employed.

We claim: 1. The azo compounds having the general formula:

X Nor'o O-N=N N wherein R represents a member selected from the group consisting of an alkyl group having 1 to 4, inclusive, carbon atoms, hydroxyalkyl group having 2 to 4, inclusive, carbonatoms, an alkoxyalkyl group having 3 to 4, inclusive, carbon atoms, a fl-cyanoethyl group, a

CH2CH2COOCH3 group, a -CH:CH2COOC2H5 group, a 2,2-difluoroethyl group, a 2,2-difiuoro-n-propyl group, a 3,3-difiuoropropyl group, a 3,3-difiuoro-n-butyl group, a 2,2,2-trifluoroethyl group and a 3,3,3-trifluoropropyl group, R1 represents a member selected from the group consisting of a hydroxyalkyl group having 2 to 4, inclusive, carbon atoms and an acetoxyethyl group, X represents a member selected from the group consisting of a hydrogen atom, a methoxy group and an ethoxy group and Y represents a member selected from the group consisting of a hydrogen atom,

a methyl group, a bromine atom, a chlorine atom, a

methoxy group, an ethoxy group, an acetylamino group,

a propionylamino group and a butyrylamino group.

2. The azo compound having the formula:

3. The azo compound having the formula:

CHzOHzOH 4. The azo compound having the formula:

omomon 5. The azo compound having the formula:

6. The azo compound having the formula:

CHaOHF, 

1. THE A ZO COMPOUNDS HAVING THE GENERAL FORMULA: 